High Resolution Infrared Studies of the Ņ2, Ņ4 Bands of 34S 16O3 Including Both Intensity and Wavenumber Perturbations

Published

April 1, 2003

Author(s)

J Barber, Tony Masiello, E T. Chrysostom, J Nibler, A G. Maki, A Weber, Thomas A. Blake, R L. Sams

Abstract

The infrared spectrum of the Ņ₂, Ņ₄ bending mode region of ³⁴S-substituted sulfur trioxide, ³⁴S ¹⁶O₃, has been recorded at a resolution of 0.0025 cm^-1. The Ņ₂ and Ņ₄ levels are coupled by a Coriolis interaction, yielding significant spectral shifts that have been successfully analyzed to obtain rovibrational constants for the ground state and both fundamentals. Comparisons are made with ³²S¹⁶O₃ parameters and the B_o rotational constant is found to be 0.348 556 04 (28) cm^-1, only very slightly larger than the corresponding value of 0.348 543 33(5) cm^-1 for ³²S¹⁶O₃. Coriolis and l-type resonance interactions between the Ņ₂ and Ņ₄ levels produce frequency shifts and strong intensity perturbations in the spectra that are considered for both ³⁴S¹⁶O₃. The resulting analysis yields an average value of 0.62(8) for the dipole derivative ratio({differential} ^x{differential}{quanternary}4x)/({differential} ^z/{differential}{quanternary}2) and a positive sign for the product of this ratio with the ζ^y2,4 Coriolis constant, for which experiment gives 0.5940(15). Ab initio calculations indicate that the signs of {differential} ^x{differential}{quanternary}_4x and {differential} ^z/{differential}{quanternary}2 are both positive and hence ζ^y2,4 is also positive, in agreement with earlier calculations. These signs indicate that the effective charge movement in the xz plane has the same sense of rotation as {quanternary} 2, {quanternary} 4x atom motion in this plane that produces a py vibrational angular momentum component, correlated motion that is confirmed by ab initio calculations.

Citation

Journal of Molecular Spectroscopy

Volume

218

Issue

No. 2

Pub Type

Journals

Keywords

infrared, spectrum, sulfur-34, surfur trioxide

Citation

Barber, J. , Masiello, T. , Chrysostom, E. , Nibler, J. , Maki, A. , Weber, A. , Blake, T. and Sams, R. (2003), High Resolution Infrared Studies of the Ņ2, Ņ4 Bands of ³⁴S ¹⁶O₃ Including Both Intensity and Wavenumber Perturbations, Journal of Molecular Spectroscopy (Accessed October 8, 2024)